Acid wool dyestuffs



Patented July 4, 1944 UNITED STATES PATENT, .oFFlcE yw m m rv rs Werner- Zerweck and Ernst Heinrich, Frankforton-tlie-Main- Fechenheim; Germany, assignors :1 l to General "Aniline &. Film Corporation, New- No Drawing application May 29, 1941, Serial No;

- g 395,787, Infiermany December 18', 1940 y i Our present invention relates to acid wool dye- -1n order to furtheri'illustrat our-inveht iohitljg,

stufis more particularly tothose of the general followingeXamples-are given,'the parts beingby formula:

weight and all temperatures in "degrees ceriti-f O k r -flbf t H l Example 1 RS933 RI 1 50 pal-a of "I-aminOQi=bromanthraquinone-2; sulfonicacid are dissol e'd inabout. 1500 parts of 1 p water and'a solution .ofl' lz [parts-oi 3.-amino-- I 1 10; benzyl-dicyclohekylainin 'ab6ut'500' parts of R: alcohol moreover 50 parts of sodium bicarbonate and parts of cuprous chloride are added thereto. The mixture is heated for some hours to boiling. After acidification the for'medi conden- R4 (SOaHL. sation product separates. lt is filtered off and a well washed out with water. wherein R1 and Rz stand for a radicle of the benparts are dlssolved m a mlxture of Zane series X for a member of the group consist 50 parts of sulfuric ac1d monohydrate and of 10 ingof alkyle'ne, O-alkylene and" s-alkylene'rad parts of fuming l 931,- Percent icles, R3 andR; fora member of the roup consiststrength The reaches P mamtameiovir ingof .alkylg cyclohexyi, benzyl aha aryi radicles mm at a temperature and we 15 of thebenzenerseries; rnumbel; from; 1064; added thereto. The separated dyestuff is filtered at the most (mean: bein resent. I off, washed with a concentrated salt solution until The process for pzod u cin g the grgsent new dye- 0 a neutral .Ieactmq a converted into the Sodium stufis according to one feature of the invention Salt by i mll it in an aqueous Sodium consists in "condensing a 1'-amino-4-halogeni gg i bt d f f ul anthraquinone-Z-sulfonic acid with'a'n amine O Y 0 0 g e i? the general formula:

wherein R2; X; R3 and R4 have the aforesaidjsignificationand generally, but not in.. al1 cases,

aftertreating the ;condensation products thus formedwith a sulfonating agent.

. In the caseof bothRsand R4 standing for aryl radicles, or R3 for benzyl and R4 for an aryl radicle, ,the condensation is advantageouslycan ried out while using an1aminocompound contain-1 ing in at least one of the radicles signified by R3 and R4 a sulfonic acidgroup. v

According to a, further feature of the invention dyestufis of the" same class are obtained by condensing a l-amino-2.4-diha1ogen-anthraquinone with an amine of the aforesaid kind and replacing in the molecule of the condensation product the halogen atom standing in'the 2.-position 'of the" anthraquinone nucleus by the sulfonic acid groupfi The'present'new dyestuffs are distinguished by I a-particular levelling power and dyewool mostly bluish shadesof good fastness properties particularly of a good fastness to lightt" 3 dyeswool reddish blue shades of agood fastness 5 5 to light, 7, It has a good levelling power.

Dyestuffs of a similar shade of likewise good fastness properties are obtained by using as second reaction component S-aminobenzyl-(methylcyclohexyD-amine or 3-amino-benzyl-(ethylcyclohexyl) amine. Dyestufi's, which dye wool somewhat more greenish blue shades are obtained when starting for instance from 2.4-dimethyl-5- amino-benzyl-(ethyl-cyclohexyl) -amine or from 4.5-dimethyl -3- amino-benzyl (dicycloheXyD- amine.

When using as component 3-aminol methoxy-benzyl- (methyl-cyclohexyl) -aminethe formed dyestuff dyes wool distinctly more greenish blue shades, and dyestuffs; which dye wool somewhat more reddish blue shades are obtained};

when starting from 2.4-dimethyl-3-amino-ben-' amino-benzyl- (dicyclohexyl) eamine.

Example 2 A mixture of a solution of 100 parts of l-amino- 4-bromo-anthraquinone-2-sulfonic acid in about 5200 parts of water. of 100 parts of sodiumbi:

carbonate, parts of copper sulfate andofan alcoholic solution of 66 parts of 3-amino-benzyl- (methyl-benzyl) -amine is heated for some hours to boiling and the formed condensation product is separated by acidification. It is filtered oil, well washed with water and dried.

By a subsequent sulfonation as described in Example 1 a dyestuff of theformula;

"15. zyl-(ethyl-cyclohexyl) -amine or ZA-dimethyl-S- Example 3 100 parts of 1-amino-4-bromanthraquinone-2- sulfonic acid are dissolved in about 5200 parts of water and a solution of 66 parts of 3-aminobenzyl-(methyl-phenyl) -amine in about 1800 parts ofzalcohol, then 100 parts of sodium bicarbonate and 10 parts of 'cuprous chloride are added. The mixture is heated to boiling for some hours. The formed condensation product is isolated as described in the foregoing examples.

10.par.ts thereof are dissolved in a mixture of 50 parts of sulfuriqacid-monohydrate and 10 parts of fuming-sulfuric acid of percent strength. The reaction massis held over night at 40 to 45 and. then ice-:isadded. The separated dyestufi is filtered oil, washed out with a concentrated salt solution until a neutral reaction and converted into the sodium salt by dissolving it in a sodium position of the benzene nucleus, moreover by starting for instance from 2.4-dimethyl-5-aminobenzyl- (methyl-benzyl) -amine, 3-amino-4-methoXy-benzyl-(methyl-benzyl)-amine or 4-aminophenetidyl- (methyl-benzyl) -amine of the formula:

' 1 dyestuffs are obtained.

bicarbonate solution.

The dyestuff thus obtained of the formula:

SOsH

dyes woolreddish blue shades of a good fastness yl-phenyD-amine of the formula:

I om.

NHz

or the corresponding thiocompound or from 3-amino-benzyl- (ethyl-phenyl) -amine, 3-aminobenzyl-(cycloheXyl-phenyl), amine, or the isomeric compounds being accordingly substituted in the 4-position of the benzene nucleus similar Dyestufis of a more greenish blue shade are obtained when starting from 2.4-dimethy-5-amino-benzyl- (methyl-phenyl) amine, 4.5-dimethyl-'3-amino-benzyl- (ethyl-phenyl) -amine, 3-amino-6-methoxy-benzyl- (methyl phenyl) amine or from 3-amino-benzyl (2'-methylphenyl-ethane-sulfonic acid) of the formula:

sponding 5-methoxy-acetylamino or 5-acetylamlno-compounds or the l-amino-4-iodinoanthraquinone-2.6-disulfonic acid with the aforesaid amino compounds.

' the case where a sulfonicacfi'd group i'spre's; e'n't'in the alkylradicle or in fi position-ofitheam thraquino'ne nucleus, a" subsequent sulfon'ation of the condensation product may be carrie'dout' or may be left'u'ndone; I Dyestuffs of a somewhat more-xfreddish blue shade are obtained when starting "from ;2'. 4,-'dimethyI-S-amino benzyl- (methyhph'enyl) amine or from 2.4 dimethyl 3 amino-benzyl-(ethylphen nj-a mine i 1 Example 4 A mixture of a solution of 100 parts of 1- amino-4-bromanthraquinone-2-sulfonic acid in about 5200 parts of water, of a solution of 72 parts of 3-amino-benzyl-(hydroxethyl-phenyl)- amine in about 1800 parts of alcohol, 100 parts of sodium bicarbonate and 10 parts of cuprous chloride is heated for some hours to boiling. The condensation is isolated as described in the foregoing examples.

10 parts thereof are dissolved in 60 parts of sulfuric acid-monohydrate and the solution is held for about 6 hours at room temperature. The formed sulfonation product is isolated as described in the foregoing examples.

The dyestuff thus obtained of the formula:

dyes wool reddish blue shades of a good fastness to light.

When carrying out the sulfonation process as described in the foregoing examples a dyestufi of the formula:

NH: H

SOaH

I. O NH of similar tinctorial properties is obtained.

When starting from 2.4-dimethyl--aminobenzyl-(hydroxethyl-phenyl) -amine or from 4.5-

rmmpzewsw SOaH dyes wool clear reddish blue shades of a good fastness to light, water, washing, Iulling, seawater and perspiration. It has a good levelling power.

When using as aminocompound the 3-aminobenzyl-diphenylamine-4'-sulfonic acid the formed dyestufl of the formula:

0 (Scan).

wherein R: stands for a phenylene radical, R3 for a member of the group consisting of alkyl.

cyclohexyl and benzyliradicais and n for a. number from l to 4, v,

obtain-able vby condensing the leamino-iebzgmnanthraquinonei-z-sulfonie acid; with 3-aminobenzyl-(methyl-benzyl) -4-amine and subjecting the formed condensation product to a. sulfona-v tion which dyestuff dyes wool clear reddish blue shades. ofa good :fastnessto light, water; washing,-,fu1l:ing', seawaten and-perspiration; and has agoodleveling power;

WERNER YZERWECK1 5 ERNST HEINRICH. 

